2,844,551 United States Patent Office Patented July 22, 1958 1. 2 Another aluminum alcoholate which can be used is 2,844,551 the so-called c-aluminum ethylate. It is readily soluble ALUMNUM COMPOUNDS AND THE PROCESS in organic solvents and can be obtained, as described by OF PREPARENGTHEM Adkins (Journal of the American Chemical Society, Vol. Ludwig Orthner and Martin Reuter, Frankfurt am Main, 44, page 2178), from amalgamated aluminum by means Germany, assignors to Farbwerke Hoechst A. G...yor of absolutely anhydrous ethanol, or as described by mas Meister Lucius & Brining, Frankfurt am Main Child and Adkins (Journal of the American Chemical Hochst, Germany, a company of Germany Society, vol. 45, page 3014), by heating sparingly soluble 6-aluminum ethylate for 15 hours to 275 C. No Drawing. Application April 7, 1953 Further aluminum alcoholates which are suitable are Seria No. 347,399 those containing per 1 equivalent of aluminum less than 1 equivalent of organic radicals which are bound in an Clains priority, application Germany April 9, 1952 ethereal manner through oxygen. 14 Claims. (C. 260-18) As such radicals there can be used aliphatic, alicyclic, 5 aromatic, araliphatic and heterocyclic hydrocarbon radi The present invention relates to aluminum compounds cals, which may, if required, be substituted by non-acid and the process of preparing them. groups such as the keto or ester group, halogen atoms From German Patent No. 569,946 it is known to such as chlorine atoms, or the amino group, or the react aluminum alcoholates with carboxylic acids in carbon chain of which may be interrupted by hetero various proportions and subsequently to hydrolyze the 20 atoms such as oxygen, sulfur or nitrogen. There may reaction products with water. Thereby, well defined pri be mentioned, for example: methyl, ethyl, chloroethyl, mary, secondary, and tertiary aluminum carboxylates are dimethyl, aminoethyl, isopropyl, butyl, octyl, octadecyl, obtained. As far as the preparation of the primary and cyclohexyl, phenyl, naphthyl, benzyl, phenylethyl, fur secondary salts of the formulae furmethyl, and the like. Several of the radicals indi 25 cated above can be bound simultaneously to the alu oH OH minum. Especially suitable aluminum alcoholates are Al-OH Aro CO-R those containing per 1 equivalent of aluminum about 0.5 O CO-R O CO-R to 0.9 equivalent of those radicals which are bound in is concerned, the corresponding mono- and di-carboxylic an ethereal way. acid aluminum alcoholates of the formulae 30 The remaining valences of the aluminum, i. e. those which are not bound in an ethereal way, by means of o R o R oxygen, to organic radicals can be saturated for example with oxygen under linkage to further aluminum atoms, AkoO CO-RR Aloco-ROCO-R 35 or with halogen, hydroxyl or organic acid radicals such are probably formed at first. By the subsequent treat as acetyl, and in this case several similar or different ment with water, the alkoxy groups are replaced by hy radicals mentioned above can simultaneously satisfy the droxy groups. remaining valences of the aluminum. Now, we have found that valuable aluminum com As aluminum alcoholates which contain per 1 equiva pounds are obtained by reacting 1 mol of aluminum al lent of aluminum less than 1 equivalent of radicals which coholate with less than 1 mol of a monobasic organic 40 are bound in an ethereal way, by means of oxygen, there substance of acid nature which forms aluminum salts, may be employed, for instance, those the solubility of or with mixtures of such substances, if desired in the which in organic solvents has been improved by thermal presence of an indifferent solvent. or hydrolytic treatment of normal aluminum alcoholates If the reaction is carried out at low temperatures it is with splitting off of a part of the alkoxy groups, in most immaterial whether the aluminum alcoholate is first in 45 cases probably with linkage of aluminum atoms by way troduced and the mono-basic organic substances of acid of oxygen atoms. nature are then added or whether the aluminum al Among these aluminum alcoholates there may be men coholate is introduced into the mono-basic organic Sub tioned, for example, the aluminum ethylates obtained by stances of acid nature or the solutions thereof. thermal treatment and corresponding to the empirical The process may also be carried out in such a way 50 molecular formulae Al(OCH5)4O and Al(OCH3)6Oa, that the reaction is performed at a low temperature, for as described by Henle (Berichte der deutschen chemischen instance a temperature below 40 C., preferably at room Gesellschaft, vol. 53, page 720); the aluminum ethylate temperature, if desired while using only part of the com obtained by hydrolytic treatment, as described in Ger ponents, and the reaction product is then heated to man Patents Nos. 277,187 and 277,188, and containing higher temperatures, if desired while adding the rest of 55 about 2 ethoxyl radicals per atom of aluminum; the basic the components. By its stepwise condensation, this proc aluminum ethylate of the empirical molecular formula ess offers the advantage of a better control of the re Al(OH) (C2H5O)2 obtained by boiling with anhydrous action and thus allows a more uniform production on an alcohol with access of air, as described by Meerwein and industrial scale. Bersin ("Annalen,” vol. 476, page 132); the aluminum-di It is also possible to perform the entire reaction at 60 hydroxocyclohexanolate obtained, as described by Meer higher temperatures. In this case it may be advan Wein and Bersin ("Annalen," vol. 476, page 132) by heat tageous to apply an elevated pressure. ing aluminum-cyclohexanolate at 275 C.; the basic alumi In practicing the present invention, suitable aluminum num ethylate obtained, as described by Bersin (Disserta alcoholates include, for example, those derived from tion Konigsberg 1928), by boiling with not absolutely an low or medium aliphatic alcohols. There are mentioned, 65 hydrous ethanol, and containing about 2 ethoxyl groups for instance: aluminum methylate, aluminum ethylate, per atom of aluminum. There may be further mentioned aluminum propylate, aluminum isopropylate, aluminum those aluminum alcoholates which can be obtained from butylate, aluminum isobutylate, aluminum amylate, alu aluminum alcoholates by reaction with slightly hydrous minum hexylate, aluminum octylate, aluminum-2-ethyl alcohols according to the process described by Tischts 70 chenko (Chem. Zentralblatt 1900, I, page 12). butylate, aluminum-2-ethylhexylate, and the like, mix There can be further used those readily soluble alumi tures of these substances or mixed aluminum alcoholates. num alcoholates which are obtained by the reaction of 2,844,551 3 4. metallic aluminum and slightly hydrous alcohols, advan wise mono-basic esters with the traces of alcohol which tageously in the presence of activating agents, and which are always present. contain per 1 equivalent of aluminum about 0.5 to 0.8 These compounds can belong to the aliphatic, isocyclic, alkoxy groups. - aromatic or heterocyclic series and can contain further As aluminum alcoholates containing halogen atoms indifferent substituents of neutral nature, for instance there may be mentioned, for instance: readily soluble halogen atoms, or groups, such as the groups OH or aluminum alcoholates containing halogen, corresponding SH, or ether, thioether or ester groups, carboxylic acid for instance to the formula AlHal(OR)2 or Al-Hals (OR), amide or urea groups or the like. This chain of carbon wherein R stands for low aliphatic radicals, such as atoms can be interrupted by heteroatoms such as O, N, AlCl(OC2H5)2, and obtainable by causing aliphatic alco or S. hols to react upon aluminum chloride, as described by As aliphatic mono-carboxylic acids may be mentioned, Mpetse (Chemisches Zentralblatt, 1931, II, 1691). for example: formic acid, acetic acid, propionic acid, Readily soluble aluminum alcoholates of that kind con butyric acid, caproic acid, caprylic acid, capric acid, taining halogen can also be obtained, according to the stearic acid, oleic acid, palmitic acid, lauric acid, myristic process described in German Patent No. 859,143, by re 5 acid, behemic acid, montanic acid, mixtures of acids ob acting a theoretically insufficient quantity of alcohols with tained by oxidation of paraffin, resin acids, such as abietic aluminum halides in the presence of ammonia or amines. acid or colophony. Instead of single acids there can also Furthermore, there may be mentioned: aluminum alco be used mixtures of the acids mentioned or mixtures holates containing halogen or being free from halogen of acids which are obtained from natural products, if and corresponding to the formula AlHal (ORC), 20 necessary hydrogenated. Mixtures of this kind are, for In-m-3, m being at least 1, R standing for an alkylene instance, the fatty acids of sperm oil, coconut oil, tall radical. These substances can be obtained by reacting oil, inseed oil, soybean oil, fish oil, cottonseed oil, train. aluminum halides with alkylene oxides, AICl(OCHCI), oil, peanut oil, sulfocarbon oil, rape oil, tallow animal for instance, can be obtained by reacting 2 moles of oil, bone fat, lard, tung oil. There may further be men ethylene oxide. with aluminum chloride. 25 tioned, for example, acrylic acid or methacrylic acid, In halogenated aluminum alcoholates of that kind, part crotonic acid, methoxyacetic acid, ethoxyacetic acid, of the radicals bound in an ether-like manner can, fur butoxyacetic acid, dodecyloxyacetic acid, chloroacetic thermore, be split off by thermal or hydrolytic after-treat acid, a-chloropropionic acid, (3-chloropropionic acid, oz ment; it is probable that in most cases the aluminum chlorobutyric acid, thioglycolic acid, thiolactic acid, atoms are linked together in chain-fashion through oxygen 30 malonic acid mono-ethyl ester, oxalic acid mono ethyl bridges. - ester, the semi-amide of malonic acid, hydantoic acid, Furthermore, there are mentioned aluminum com glycolic acid, lactic acid, 8-hydroxybutyric acid, the mono pounds obtainable by thermal and/or hydrolytic treat ethyl ester of maleic acid, propylsulfamido acetic acid, ment of carboxylic acid aluminum dialcoholates. This dodecylsulfamido acetic acid, and mixtures of aliphatic reaction leads to a partial separation of alkoxyl radicals 35 alkylsulfamido acetic acids. and, probably, to the formation of chains between the As alicyclic mono-carboxylic acids can be used, for aluminum atoms by means of the oxygen atoms. There instance: cyclopentane-carboxylic acid, cyclohexane-car by carboxylates of complex aluminum alcoholates of the boxylic acid, hexahydro-salicylic acid or analogous acids. formula AlAcyl(OR)O in which the sum of x and y As aromatic mono-carboxylic acids are mentioned, for and z reaches the value of 2.5-3, for instance 40 instance: benzoic acid ortho-chlorobenzolic acid, 4-chloro benzoic acid, 2-methyl-benzoic acid, 3-methyl-benzoic Al(OCH5)(CH3COO)1Oos acid, 4-methyl-benzoic acid, ox-naphthoic acid, g-naphthoic are for example obtained. acid, ox-naphthoxy acetic acid, (3-naphthoxy-acetic acid, There can also be used mixtures of aluminum alco phenyl-acetic acid, cinnamic acid, phthalic acid-mono holates having a reduced content of alkoxyl or mixtures 45 ethyl ester, salicylic acid, 2.3-hydroxynaphthoic acid, 3 of these alcoholates with normal aluminum alcoholates hydroxybenzoic acid, 4-hydroxybenzoic acid, methoxy containing 3 alkoxyl groups. benzoic acid, phenoxy-acetic acid, 2.4-dichlorophenoxy Instead of the aluminum alcoholates, the products ob acetic acid, the semi-amide of phthalic acid, paratoluene tained by addition of carbon dioxide or sulfur dioxide sulfamido-acetic acid, and the like. As heterocyclic mono to these alcoholates can also be used for the preparation 50 carboxylic acids may be mentioned, for example: py of the solutions of the aluminum alcoholates. (Cf. romucic acid, nicotinic acid, thiophene-ox-carboxylic acid, Tischtschenko, Chemisches Zentralblatt 1900, I, page 2-hydroxy-carbazole-3-carboxylic acid, 3-hydroxy-di 585.) The said addition products are advantageously phenylene-oxide-2-carboxylic acid, 1-phenylpyrazolone used whenever they are more stable in storage than the (5) - 3 - carboxylic acid, 5 - benzoyl-benzoxazolone-2- alcoholates themselves. When dissolving the addition 55 carboxylic acid, 3 -hydroxy-2-methyl-quinoline-4-carb compounds in inert solvents, especially in the heat, car oxylic acid, pyrrole-a-carboxylic acid, 8-indolyl-acetic acid. bon dioxide or sulfur dioxide splits off and the alcoholates are regenerated. For the reaction with the aluminum alcoholate car The aluminum alcoholates can also be used in the form boxylic anhydrides can also be used according to the of their alkoxo acids and/or in a form stabilized against process described in German Patent No. 853,354, such as moisture by means of volatile organic substances capable 60 acetic anhydride, propionic anhydride, lauric anhydride, of forming complex compounds. benzoic anhydride, stearic anhydride, phthalic anhydride, As mono-basic organic substances of an acid nature succinic anhydride, maleic anhydride, 4-chlorophthalic capable of forming salts with aluminum and suitable for anhydride, 3.6-dichlorophthalic anhydride, tetrachloro the manufacture of reaction products with aluminum al phthalic anhydride, tetrahydrophthalic anhydride and coholate, there may be mentioned, for example: mono 65 similar products obtained by the diene-synthesis with carboxylic acids, mono-sulfinic acids, mono-sulfonic acids, maleic anhydride. Furthermore, mono-basic diacyl mono-sulfuric acid esters, mono-sulfamic acids, mono amides of carboxylic acids, such as diacetamide, dilauryl basic phosphonic acids, mono-basic phosphoric acid esters, amide, dibenzamide, phthalimide and the like may also diacylamides containing carboxyl and/or sulfonyl radi be used. cals, sulfamides and the like. Instead of mono-car 70 As organic mono-sulfinic acids enter into consideration, boxylic acids, their anhydrides can be used as well, be for instance: the sulfinic acids of ethane, propane, do cause they are converted into free acids and indifferent decane, cyclohexane, benzene. esters with the traces of alcohol which inevitably adhere to As organic mono-sulfonic acids may be mentioned, for the aluminum alcoholates. Instead of mono-basic esters example: propanesulfonic acid, dodecanesulfonic acid, dicarboxylic anhydrides can also be used which form like 75 cyclohexanesulfonic acid, benzenesulfonic acid, para 2,844,551. 5 6 toluene-sulfonic acid, naphthalenesulfonic acid, octyl As volatile organic substances capable of forming benzene-sulfonic acid, butylnaphthalene-sulfonic acid, hy complex compounds there may be mentioned: compounds droxyethane-sulfonic acid, phenolsulfonic acid, naphthol containing a feebly acid group, for instance, aliphatic sulfonic acid, 2-hydroxy-carbazole - 7 - sulfonic acid, hydroxycarboxylic acid esters such as tartaric acid di thiophene-a-sulfonic acid. There can, furthermore, be ethyl ester, or oximes, for instance acetone-oxime, used the mono-basic amides and imides of sulfonic acids acetaldehyde-oxime; furthermore, compounds containing of the said kind, such as dodecanesulfamide, benzene a group capable of desmotropic rearrangement to the sulfamide, para-toluenesulfamide, benzene-disulfimide, aciform, for instance, acetylacetone, acetoacetic ester, para-toluene-disulfimide, dodecanedisulfimide, propane malonic acid dinitrile, nitromethane, nitropropane or the sulfamide, propane-disulfimide. O like; furthermore, compounds containing a reactive There can also be applied, for instance, the mono-basic methylene group, for instance malonic acid esters; hy sulfinic and sulfonic acids, the sulfamides and sulfimides droxy-oxo-compounds such as butyroin and aliphatic from mixtures of hydrocarbons of middle or higher molec nitriles such as acetonitrile, enter also into consideration. ular weight which can be obtained, for example, by As indifferent solvents there may be used chlorinated known processes from the sulfochlorides of fossil and 5 hydrocarbons or hydrocarbons such as benzine, benzene, synthetic diesel oils or by sulfonation of petroleum dis xylene, carbon tetrachloride, trichlorethylene, perchlor tillates an dalkylbenzenes. ethylene, chlorobenzene, furthermore, esters of low As mono-sulfuric esters are mentioned, for instance: boiling point such as ethyl acetate, amyl acetate, dialkyl ethylsulfuric acid esters, butylsulfuric acid esters, do ethers such as diethyl ether, cyclic ethers such as dioxan decylsulfuric acid esters, cyclohexylsulfuric acid esters, 20 or the like. phenylsulfuric acid esters, alkylphenylsulfuric acid esters, In the reaction of the aluminum alcoholates with the stearylsulfuric acid esters, benzylsulfuric acid esters. mono-basic organic compounds having an acid nature As mono-basic organic sulfamic acids may be men and forming salts with aluminum it is most probable tioned for example: ethylsulfamic acid, dodecylsulfamic that the acid aluminum alcoholate at first formed by acid, cyclohexylsulfamic acid, phenylsulfamic acid. 25 replacement of an alkoxy group by the equivalent Furthermore, there come into question, for example, quantity of acid radicals, reacts with the aluminum mono-basic acid cyclic imides: benzoic acid sulfimide, alcoholate in excess whereby filamentary molecules may barbituric acid, ethylbarbituric acid. be formed which, if desired, can be cross-linked further As mono-basic organic phosphonic acids can be used, more. According to the molecular proportion of the for instance: the mono-esters of phosphonic aliphatic or 30 reaction components and the reaction conditions, the alicyclic alcohols, such as the mono-ethylester of the number of the ether and acid radicals present may vary. cyclohexane-phosphonic acid of the formula When working at lower temperatures, the chain-length and the degree of the formation of cross-linkages seem and the corresponding amyl ester, the ethyl, amyl, dodecyl, 35 to be far inferior to those obtained when working at or cyclohexyl esters of hexanephosphonic acid, or the higher temperature so that the resultant products dissolve ethyl, butyl, dodecyl, or cyclohexyl esters of phenylphos more readily in organic solvents. phonic acid. The great number of aluminum alcoholates and mono As mono-basic phosphoric acid esters are used, for basic organic acid substances or their derivatives which example: the dialkyl esters of phosphoric acid of the 40 are suitable for the present reaction allows of adapting formula PO(OR)2CH R=aliphatic or alicyclic radical in a very favorable way the properties of the resultant such as the diethyl, dibutyl, diamyl, didodecyl, dibenzyl, organic aluminum compounds to the uses to which they dioctadecyl or dicyclohexyl esters of phosphoric acid. are to be put. The aluminum compounds obtained have There can also be used mixtures of these compounds; an oily to semisolid or a waxy or resin-like consistency. it is also possible to react several compounds one after They are soluble in many organic solvents and com the other with the aluminum alcoholate, for instance, first patible with plasticizers. They can be applied on a acetic acid, then benzoic acid or 2.3-hydroxy-naphthoic technical scale for many purposes, for instance, in the acid. lubricant, propellant, and varnish industries. The gradual use of the said acid organic compounds Reference is made to our patent application Serial No. and carboxylic acids of high molecular weight in the re 50 347,400, entitled "Process for Rendering Fibrous Ma action with the aluminum alcoholate is of particular ad terials Water-Repellent,” filed April 7, 1953, now U. S. vantage. Thus it is possible, for instance, to react the Patent No. 2,801,190, issued July 30, 1957. latter first with 0.2-0.8 mol of acetic acid and then with The following examples serve to illustrate the inven 0.1-0.7 mol of stearic acid, however, only with at most partstion butbeing they by weight:are not intended to limit it thereto; the about 0.9 mol of acid in total. 55 Particularly valuable products, i. e. products which Example 1 are to a far-reaching extent stable to moisture, especially at ordinary temperature, are obtained by treating the To 104 parts (F0.64 mol) of aluminum ethylate dis reaction products with volatile organic compounds solved in 634 parts of ethyl acetate there are added 80 capable of forming complex compounds. These com 60 parts (F0.29 mol) of stearic acid (solidification point pounds can also be added before or during the reaction 55 C., molecular weight 272) and the mixture so ob of the alcoholates with the mono-basic organic substances tained is boiled for 1 hour under reflux. Then the having an acid nature and forming salts with aluminum. solvent is distilled off, at first under atmospheric pres The products thus obtained are stable to atmospheric Sure and subsequently under reduced pressure. A residue moisture and water at low temperatures; the reaction 65 of 162 parts of a soft wax is obtained which is soluble products obtained from aluminum alcoholates and the in hot carbon tetrachloride. said mono-basic organic compounds of acid nature and stabilized to a far-reaching extent may, under certain Example 2 circumstances, even be used in an aqueous medium To 50 parts (-0.31 mole) of aluminum ethylate dis without hydrolytic cleavage taking place at low tempera 70 Solved in 300 parts of ethyl acetate there are added 60 tures. The above-mentioned substances capable of form parts (F0.22 mol) of commercial stearic acid (solidi ing complex compounds are advantageously added in the fication point 55 C., molecular weight 272) and the liquid or the dissolved state at ordinary or raised tem mixture so obtained is boiled for 2 hours under reflux, peratures in quantities of about 0.1-2 mols according The solvent is then distilled off, at first under normal to the desired degree of stabilization. 75 pressure and subsequently under reduced pressure. A 2,844,551 7 - 8 residue of 89 parts of a soft, tough resin is obtained eliminated chlorethyl alcohol are then distilled off, at which is soluble in hot carbon tetrachloride. first under normal pressure and finally under reduced Example 3 pressure while taking care that the temperature in the reaction product or mixture rises to 120° C. 128 parts (=0.63 mol) of aluminum isopropylate are 5 The condensation product of aluminum chlorethylate dissolved in 280 parts of benzene and then 100 parts and stearic acid remains as a yellowish, thick oil which (=5.35 mol) of stearic acid (solidification point 65 C., solidifies slowly at room temperature to a soft wax which molecular weight 282) are added and the mixture so is easily soluble at room temperature, for example, in obtained is boiled for 1 hour under reflux. The solvent carbon tetrachloride, benzene and test benzine. is then distilled off, at first under normal pressure and 0. When proceeding in the same manner as described subsequently under reduced pressure. A residue of 180 above but using, instead of the aluminum chlorethylate, parts of a viscous oil is obtained which is soluble in cold 411 parts of aluminum dichloropropylate produced in the carbon tetrachloride and in hot benzene and hot petro same way from aluminum chloride and 3 mols of epichlo leum ether. rohydrin or 308 parts of aluminum bromopropylate pro Example 4 5 duced from aluminum bromide and 3 mols of propylen 150 parts (=0.57 mol) of sperm oil fatty acid (acid oxide, analogous condensation products of aluminum number 212, iodine number 70.5) are added to 104 parts alcoholate and stearic acid are obtained. (=0.64 mol) of aluminum ethylate dissolved in 634 . . When instead of stearic acid, 240 parts of commercial parts of ethyl acetate and the mixture so obtained is sperm oilfatty acid (acid number 212, saponification num boiled for 1 hour under reflux. The solvent is then 20 ber 214, iodine number 71) are reacted in the manner distilled off, at first under normal pressure and finally described above with aluminum chlorethylate, the con under reduced pressure. A residue of 215 parts of a densation product of aluminum chlorethylate and sperm soft, tough wax is obtained which is soluble in hot carbon oil fatty acid is obtained as a viscous oil at normal tem tetrachloride. perature; it likewise dissolves readily in carbon tetra Example 5 25 chloride, benzene, and test benzine. 110 parts of stearic acid (solidification point 55 C., Example 8 molecular weight 270) are dissolved at 40 C., while 120 parts of aluminum methylate are dispersed, while stirring, in 1100 parts of a solution of commercial alumi stirring, in 3000 parts of benzene, 250 parts of stearic acid num ethylate in ethyl acetate (2.2 percent Al) obtained 30 (solidification point 52 C., molecular weight 278) are according to German Patent No. 386,688. The mixture added and the mixture so obtained is boiled for 1 hour thus obtained is then boiled for 2 hours under reflux, and under reflux. Methanol separates and a viscous solution subsequently the solvent is distilled off, first under nor of the condensation product of aluminum methylate and mal pressure and finally under reduced pressure. 225 stearic acid is obtained. The solvent and the separated parts of a viscous oil are obtained which, at room tem 35 methanol are then distilled off under reduced pressure perature, solidifies to a tough wax and is soluble in hot and an elastic resin is obtained as residue which is soluble carbon tetrachloride and benzene. in benzene, xylene and perchlorethylene. When proceeding in the same manner but using, in When proceeding in the same manner but using, instead stead of the stearic acid, 191 parts of sperm oil fatty of the stearic acid, an equal amount of oleic acid (solidi acid (acid number 212, saponification number 214, iodine 40 fication point --10 C.) or abietic acid or colophony or number 71) 580 parts of a viscous oil are obtained which else 335 parts of montanic acid (molecular weight 372), still contains a little ethyl acetate. This product solidi the condensation product of aluminum methylate and fies at room temperature with formation of a gelatin oleic acid or abietic acid or montanic acid, respectively, which, after being caused to swell, is soluble in hot carbon is obtained as a resin which is likewise soluble in xylene. tetrachloride. 45 Example 6 Example 9 120 parts of stearic acid (solidification point 55 C., 246 parts of aluminum-n-butylate are dissolved, while molecular weight 270) are dissolved at 40 C., while stirring, in 1000 parts of hot n-butanol and 100 parts of stirring, in 1100 parts of a solution of commercial alumi a mixture of fatty acids obtained by oxidation of paraffin num ethylate in ethyl acetate (2.2 percent Al) obtained (average molecular weight 170, solidification point 27 according to German Patent No. 386,688. The mixture C.) are added to the solution at 50° C. Butanol separates is then boiled for 1 hour under reflux and to the clear and a clear solution of the condensation product of alu solution thus obtained 110 parts of commercial castor minum butylate and the fatty acid mixture above men oil fatty acid (acid number 178, saponfication number tioned is obtained. This solution is boiled for 1 hour 197, iodine number 85, 2.2 percent OH) are added at 70 5 5 under reflux. After distilling off the butanol under re C., while stirring, and the mixture is again boiled for duced pressure, an oil solidifing in the form of a wax is 1 hour under reflux. The solvent is then distilled off, obtained as residue which is soluble in xylene and per finally under reduced pressure. A yellowish, soft, rub chlorethylene. ber-like resin is obtained which is soluble in cold benzene When proceeding in the same manner, but using in while swelling. 60 stead of the above fatty acid mixture the corresponding When proceeding in the same manner but using, in amount of naphthenic acid (acid number: 356), the con stead of the solution of commercial aluminum ethylate in densation product of aluminum butylate and naphthenic ethyl acetate, 1800 parts of a 10 percent solution of acid is obtained in the form of a wax which is soluble aluminum isopropylate in benzene, 420 parts of a soft, in xylene and perchlorethylene. rubber-like resin are obtained which, after being caused to swell at room temperature, is soluble in hot benzene. Example 10 Example i 27 parts of commercial fatty acid from sperm oil are dissolved at 20° C., while stirring, in 200 parts of a 10 266 parts of aluminum chlorethylate obtained from percent solution of aluminum ethylate in xylene. After aluminum chloride and 3 mols of ethylene oxide are allowing the whole to stand for 12 hours at 20° C., the dissolved at 60° C. in 800 parts of benzene and then 140 solution is heated at 45 C. for 10 hours in the absence parts of commercial stearic acid (solidification point 52 of air and moisture. After distilling off the solvent under C.) are added while stirring. A clear solution of a con reduced pressure, a tough wax is obtained which dissolves densation product of aluminum chlorethylate and stearic while swelling at room temperature in carbon tetrachloride acid is obtained. From this solution the benzene and the 5 and benzene and yields viscous solutions. 2,844,551 9 10 Example II tion product of chloroacetic or thioglycollic aluminum 1100 parts of a solution of the condensation product isopropylate and stearic acid is obtained in the form of of aluminum ethylate and stearic acid in ethyl acetate, elastic resins which are soluble in test benzine and Xylene. which solution has been prepared by reacting for 3 hours Example 15 at 20° C. 0.8 mol of stearic acid with commercial alumi num ethylate solution in ethyl acetate (prepared accord 30 parts of glacial acetic acid are added drop by drop ing to the German Patent No. 386,688 and containing at about 30 C., while stirring and cooling, to 1000 parts 2.2 percent Al), are heated for 4 hours to 40 C. The of a solution of commercial aluminum ethylate in ethyl solvent is then distilled off at 60° C. A tough wax is ob acetate (2.7 percent Al), prepared according to German tained which is soluble in carbon tetrachloride, benzene Patent No. 386,688. In the clear solution of acetic alumi and benzine and can be molten with paraffin hydrocar num ethylate thus obtained there are dissolved at about bons with formation of homogeneous products. 50 C., while stirring, 110 parts of commercial stearic acid (molecular weight 275, solidification point 52 C.) Example 12 and the clear solution of the condensation product of ace 7 parts of stearic acid are dissolved at 50° C. in 210 5 tic aluminum ethylate and stearic acid is boiled for 1 parts of a benzene solution of the condensation product hour under reflux. After distilling off the ethyl acetate of aluminum isopropylate and oleic acid produced by and the eliminated ethyl alcohol, a soft resin is obtained causing to react for 1 hour at 20 C. 13.5 parts of oleic as residue which is soluble in carbon tetrachloride, ben acid with the solution of 20 parts of aluminum isopro zene, xylene, and test benzine. pylate in 176 parts of benzene. The solution so obtained 20 By using, instead of the stearic acid, 80 parts of lauric is then boiled for 1 hour under reflux and subsequently acid or, instead of the glacial acetic acid, 23 parts of the solvent is distilled off, finally under reduced pressure. formic acid, and proceeding otherwise in the same man A highly viscous, yellowish oil is obtained which solidifies ner, the condensation product of acetic or formic alumi at room temperature. The product is soluble in carbon num ethylate and lauric acid or stearic acid, respectively, 25 is obtained in the form of resins which are soluble in tetrachloride and benzene. Xylene. Example 13 Example 16 204 parts of aluminum isopropylate are dissolved in a 40 parts of acetic anhydride are added drop by drop, mixture of 800 parts of isopropanol and 800 parts of while stirring, at about 30° C. to 1000 parts of commer xylene and to this solution 48 parts of glacial acetic acid 30 cial aluminum ethylate dissolved in ethyl acetate (2.7 diluted with 500 parts of xylene are added drop by drop, percent Al). Spontaneous heating of the solution takes while stirring, at 30° C. Slight spontaneous heating of place and ethyl acetate is split off. A clear solution of the reaction mixture takes place and a clear solution of the acetic aluminum ethylate is obtained, in which 110 the condensation product of aluminum isopropylate and parts of palmitic acid are dissolved, while stirring, at acetic acid is obtained. By stirring for 1 hour at 80 35 about 40° C.; the clear solution is boiled under reflux C. a viscous solution is obtained which, after removal of for a further hour. The solvent is then distilled off yield the solvent by distillation under reduced pressure at about ing the condensation product of acetic aluminum ethylate 90° C., yields the condensation product of aluminum iso and palmitic acid in the form of a tough wax, which is propylate and glacial acetic acid in the form of a brit soluble in carbon tetrachloride, test benzine, and Xylene. tle resin which is soluble in benzene and xylene. By us 40 By using, instead of acetic anhydride, 50 parts of ing, instead of glacial acetic acid, 75 parts of chloroacetic propionic anhydride or, instead of palmitic acid, stearic acid, and proceeding otherwise in the same manner, the acid, and proceeding otherwise in the same manner, the condensation product of aluminum isopropylate and chlo condensation product of propionic or acetic aluminum roacetic acid is obtained in the form of a brittle resin ethylate and palmitic acid or stearic acid, respectively, is which is soluble in benzene, xylene and carbon tetrachlo 45 ride. obtained as a wax which is soluble in Xylene. Example 17 Example 14 1476 parts of aluminum-n-butylate are dissolved in 204 parts of aluminum isopropylate are dissolved in 4000 parts of benzene; in this solution 366 parts of benzoic 1000 parts of xylene and at about 30° C. a solution of 30 50 acid are dissolved, while stirring, at 40 C. and the parts of glacial acetic acid in 500 parts of xylene is run solution thus obtained is stirred at 70° C. for a further in, while stirring and cooling from outside. A viscous hour. A viscous solution of the condensation product of solution of a condensation product of aluminum isopro aluminum butylate and benzoic acid is obtained. After pylate and acetic acid is obtained in which 120 parts of distilling off the benzene and the eliminated butanol, commercial stearic acid (molecular weight 270, solidifica 55 the product is obtained as a brittle resin which is soluble tion point 52 C.) are dissolved at 70° C., while stir in xylene. By using, instead of benzoic acid, 471 parts ring. After the xylene and the eliminated isopropanol of 4-chlorobenzoic acid or 516 parts of a-naphthoic acid, have been distilled off under reduced pressure, the con the condensation product of aluminum butylate and 4 densation product of acetic aluminum isopropylate and chlorbenzoic acid or ce-naphthoic acid is obtained as a stearic acid is obtained in the form of an elastic resin 60 resin which is soluble in Xylene. which is soluble in aliphatic and aromatic hydrocarbons, The resin of aluminum butylate and benzoic acid can such as test benzine and xylene. also be produced without the addition of a solvent, by By using, instead of stearic acid, and equal amount of introducing, while stirring, the benzoic acid into the commercial fatty acid from sperm oil (acid number 210; molten aluminum butylate, stirring the melt for a further saponification number, 214; iodine number, 71) or 60 65 parts of an American naphthenic acid of the average hour, and subsequently distilling off the butanol which molecular weight of 170, and distilling at 150 C-160 has been eliminated. C./12 mm., and proceeding otherwise in the same manner, Example 18 the condensation product of acetic aluminum isopro 102 parts of aluminum isopropylate are dissolved in pylate and the fatty acid from sperm oil or naphthenic 70 1000 parts of boiling isopropyl alcohol; the solution acid, respectively, is obtained in the form of resins which thus obtained is cooled to about 40° C. and 120 parts of are soluble in aromatic hydrocarbons. dibenzene sulfimide are dissolved therein, while stirring. By using, instead of glacial acetic acid, 45 parts of A clear solution of the condensation product of alumi chloroacetic acid or 46 parts of thioglycollic acid, and num isopropylate and dibenzene sulfimide is obtained proceeding otherwise in the same manner, the condensa 75 which is boiled for a further hour under reflux. After 2,844,551 m 1. . . . 12. distilling off the isopropanol and cooling, a soft resin ate and the respective esters of the phosphonic acids are is obtained as residue which is soluble in chlorinated obtained in the form of resin-like substances, soluble aliphatic hydrocarbons, such as carbon tetrachloride, and in Xylene. in aromatic hydrocarbons, such as benzene and xylene. Example 22 By using, instead of dibenzene-sulfimide, 32 parts of di-para-toluene-sulfimide, and proceeding otherwise 204 parts of aluminum isopropylate are dissolved in in the same manner, the condensation product of alumi 1000 parts of xylene, and the solution of 105 parts of num isopropylate and di-para-toluene-sulfimide is ob di-n-butyl ester of phosphoric acid of the formula tained as a resin which is soluble in carbon tetrachloride PO(OCH)OH and Xylene. O Example 19 in 500 parts of xylene is added at about 30° C. The clear To 1000 parts of a solution of commercial aluminum solution is then heated for 1 hour to about 70° C. The ethylate in ethyl acetate (2.7 percent of aluminum), solvent is distilled off under reduced pressure, and the diluted with 1000 parts of anhydrous alcohol, 124 parts condensation product of aluminum isopropylate and the of salicylic acid are added, while stirring, at about 20 C., dibutyl ester of phosphoric acid is obtained in the form and the mixture is boiled for 1 hour under reflux. A of a wax which is soluble in aliphatic and aromatic clear solution of the condensation product of aluminum hydrocarbons and chlorinated hydrocarbons. ethylate and salicylic acid- is formed. The solvent and When proceeding in the same manner but using, in the eliminated ethanol are removed by distillation under stead of the dibutyl ester, 77 parts of diethyl ester or reduced pressure, and a brittle resin is obtained which is 20 119 parts of diamy ester or 217 parts of di-dodecyl ester soluble in ethyl acetate and alcohol. or 301 parts of di-octadecyl ester or 138 parts of di When proceeding in the same manner but using, instead benzyl ester of phosphoric acid, the corresponding con of salicylic acid, 170 parts of 2-hydroxynaphthalene-3- densation products of aluminum isopropylate and the carboxylic acid, the condensation product of aluminum respective esters of the dialkylphosphoric acid are ob ethylate and the 2-hydroxynaphthalene-3-carboxylic acid 25 tained in the form of waxes which are soluble in aliphatic is obtained in the form of a resin soluble in ethyl acetate or aromatic hydrocarbons and chlorinated hydrocarbons. and alcohol. m Example 23 Example 20 To 1000 parts of a solution of commercial aluminum To 1000 parts of a solution of commercial aluminum 30 ethylate in ethyl acetate (2.7 percent of aluminum) a solu ethylate in ethyl acetate (2.7 percent of aluminum) tion of 72 parts of anhydrous actic acid in 600 parts of there is added, while stirring, the solution of 86 parts anhydrous alcohol is added at about 30 C., while stirring. of para-toluenesulfonic acid in 800 parts of anhydrous The clear solution of the condensation product obtained is alcohol. The resultant solution of the condensation boiled for 1 hour under reflux. The solvents are then product is boiled for 1 hour under reflux. The solvents 35 distilled off, and a brittle resin is obtained as residue are then distilled off from the clear solution, finally which is soluble in anhydrous alcohol. under reduced pressure. As residue the condensation When proceeding in the same manner but using, in product of aluminum ethylate and para-toluene-sulfonic stead of lactic acid, 51 parts of anhydrous glycollic acid acid is obtained in the form of a brittle resin soluble in or 83 parts of 6-hydroxybutyric acid, the condensation anhydrous alcohol. 40 product of aluminum ethylate and glycolic or hydroxy When proceeding in the same manner but using, instead butyric acid is obtained in the form of a resin soluble in of para-toluenesulfonic acid, 80 parts of benzensulfonic anhydrous alcohol. acid or 160 parts of an alkyl sulfonic acid of the average When proceeding in the same manner but using only 36 molecular weight of 300 obtained in known manner parts of lactic acid and subsequently adding 112 parts of from a mixture of synthetic hydrocarbons (distilling over Stearic acid, the condensation product of lactic aluminum between 230° C. and 320° C., and having carbon atom ethylate and stearic acid is obtained as a brittle resin chains of an average length of about C16, and an average which is soluble in anhydrous alcohol. molecular weight of about 220), by semisulfochlorina tion of these hydrocarbons followed by hydrolysis to the Example 24 sulfonic acid and separation of the unsaponifiable mat 50 To a solution of 245 parts of aluminum-n-butylate in ter, the condensation product of aluminum ethylate 840 parts of xylene there are added, while stirring, at and benzenesulfonic acid or alkylsulfonic acid is obtained about 50 C., 114 parts of benzenesulfinic acid which has in the form of resins soluble in alcohol. been prepared recently, whereby a clear solution of the condensation product of aluminum butylate and benzene Example 21 55 Sulfinic acid is formed with elimination of butanol. The To 1000 parts of a solution of commercial aluminum solvent is distilled off at about 70° C. under reduced ethylate in ethyl acetate (2.7 percent of aluminum) there pressure (10 millimeters of mercury), and a soft resin is added, while stirring, at temperatures from about is obtained as residue which is solubie in Xylene, benzene, 20 C. to about 30° C., the solution of 124 parts of the carbon tetrachloride and ethyl acetate. mono-2-ethylbutyl ester of cyclohexanephosphonic acid, 60 When proceeding in the same manner but using, in corresponding to the formula CHPO(OCH) OH, in stead of benzenesulfinic acid, 112 parts of cyclohexane 500 parts of ethyl acetate, and the clear mixture is sulfinic acid or 78 parts of para-toluenesulfinic acid or boiled for 1 hour under reflux. From the clear solution 240 parts of alkylsulfinic acid of an average molecular of the condensation product thus obtained the solvent is 65 weight of 280 obtained in known manner from a hydro distilled off, and the product is obtained as a brittle resin carbon fraction, produced by hydrogenation of carbon which is soluble in carbon tetrachloride, test benzine and monoxide by the Fischer-Tropsch method (distilling at xylene. temperatures between 230 C. and 320° C. and having When proceeding in the same manner but using, in an average molecular weight of about 220 and an average stead of the mono-2-ethyl-butyl ester, 95 parts of mono 70 chain length of about C16), by semisulfochlorination, re ethyl ester or 117 parts of mono-amyl ester or 116 parts action with sodium sulfite, and separation of the un of mono-dodecylester of cyclohexane-phosphonic acid or saponifiable matter), the condensation product of alumi the corresponding 'amounts of the same mono-esters of num butylate and cyclohexane or para-toluene or alkyl phenylphosphonic acid or hexanephosphonic acid, the sulfinic acid is obtained in the form of a soft resin soluble corresponding condensation products of aluminum ethyl 75 in Xylene. 2,844,551 13 14 Example 25 of pyromucic acid, the condensation products of alumi 246 parts of aluminum-n-butylate are dissolved with num ethylate and succinimide or pyromucic acid are 1000 parts of hot anhydrous n-butanol, and 120 parts of obtained in the form of brittle resins which are soluble phthalic anhydride are added, while stirring, at about in anhydrous alcohol. 60° C. A clear solution of the condensation product of Example 29 aluminum butylate and mono-butyl ester of phthalic acid is obtained, which is heated for 1 hour at about 100° C. 204 parts of aluminum isopropylate are dissolved in The butanol is distilled off, finally under reduced pres 1000 parts of xylene, 225 parts of n-dodecanesulfamide sure, and a resin is obtained as residue which is soluble are added, while stirring, and the mixture is boiled for in butanol, carbon tetrachloride, benzene and xylene. 0. 1 hour under reflux, while stirring. Isopropanol is split When proceeding in the same manner but using, in off and a clear solution of the condensation product of stead of phthalic anhydride, 150 parts of 4-chloro-phthalic aluminum isopropylate and dodecanesulfamide is formed. anhydride, the condensation product of aluminum butyl The solvent is distilled off, finally under reduced pres ate and mono-butyl ester of chlorophthalic acid is ob sure, and as residue an oil is obtained that solidifies to tained as a resin which is soluble in butanol. 5 a wax readily soluble in carbon tetrachloride and xylene. When proceeding in the same manner but using, in When instead of n-dodecanesulfamide 150 parts of Stead of aluminum butylate dissolved in butanol, 1000 paratoluenesulfamide are used, the condensation prod parts of a solution of commercial aluminum ethylate in uct of aluminum isopropylate and toluenesulfamide is ethyl acetate (2.7 percent of aluminum) and adding 1000 obtained in the form of a wax which is soluble in anhy parts of anhydrous alcohol, the condensation product of 20 drous alcohol, xylene and perchlorethylene. aluminum ethylate and mono-ethyl ester of phthalic acid When proceeding in the same manner but using, in is obtained in the form of a brittle resin soluble in stead of n-dodecanesulfamide, 500 parts of a mixture ethanol. of aliphatic sulfamides, obtainable in known manner Example 26 from a synthetic diesel oil (distilling at a temperature 25 between about 200 C. and about 250° C. and having In 1000 parts of a solution of commercial aluminum an average chain length of about C16) by semisulfo ethylate in ethyl acetate (2.7 percent of aluminum) 200 chlorination, formation of amide without separation of parts of benzoic anhydride are dissolved, while stirring, the unsaponifiable matter (content of disulfamide=11 at about 20° C. Ethylbenzoate is split off and a clear percent), an oily and viscous solution of the conden solution of the condensation product of aluminum ethyl 30 sation product of aluminum isopropylate and alkylsulfa ate and benzoic acid is obtained, which is boiled for 1 mide in diesel oil is obtained, which solution forms clear hour under reflux. First the solvent is distilled off and, mixtures with test benzine, xylene and perchloroethylene. finally, under reduced pressure (0.5 millimeter of mer cury), the benzoic acid ethyl ester. The condensation Example 30 product is obtained in the form of a resin which is soluble 35 29 parts of aluminum ethylate, dissolved in 293 parts in carbon tetrachloride and xylene. of xylene are cooled in an autoclave provided with a When proceeding in the same manner but using, in stirring device, by external cooling to --2 C. To the stead of benzoic anhydride, 500 parts of stearic anhy solution obtained there is added in the course of 1 hour dride, the condensation product of aluminum ethylate and while stirring the solution of 45 parts of stearic acid and stearic acid is obtained as a resin soluble in xylene. 40 in 80 parts of xylene, the temperature being kept at about --5 C. by external cooling. When the addition Example 27 has been terminated, stirring is continued over night 120 parts of aluminum methylate are boiled, while without external cooling, whereby the temperature rises stirring, for 1 hour under reflux in 3000 parts of benzene to about +20° C. with partial separation of the reac With 36 parts of glacial acetic acid, whereby methanol is 45 tion, product. The solvent is then distilled off under split off and a viscous solution of acetic aluminum methyl reduced pressure, the temperature of the sump being ate is formed. 81 parts of stearic acid (solidification maintained at about 20° C. There are obtained 57 point 50 C., molecular weight 270) are then added, parts of a yellowish, tough, wax-like substance which is while stirring, at about 70° C., and the mixture is boiled soluble in cold carbon tetrachloride, benzine, benzene for a further hour under reflux. Methanol is split off 50 and ether. and a viscous solution of the condensation product of Example 31 acetic aluminum methylate and stearic acid is formed. The solvent and the methanol are distilled off, and an In a vessel provided with a stirrer and external cooling elastic resin is obtained which is soluble in xylene, ben 135 parts of commercial oleic acid (molecular weight Zene and perchlorethylene. 270, iodine number 85) are added, at 15° C.-20 C., to 55 204 parts of aluminum isopropylate, dissolved in 2000 When proceeding in the same manner but using, in parts of benzene, and the mixture is stirred for 10 hours. stead of stearic acid, the corresponding amount of oleic A viscous clear solution of the condensation product of acid or abietic acid or colophony or 100 parts of mon aluminum isopropylate and oleic acid in benzene is ob tanic acid (molecular weight 335), the condensation tained. When the benzene is distilled off under reduced product of acetic aluminum methylate and oleic or abietic 60 pressure at room temperature, 310 parts of a brittle wax or montanic acid is obtained in the form of a resin like white substance are obtained which is soluble in soluble in xylene. cold benzene, swells in cold carbon tetrachloride and is Example 28 insoluble in benzine. To 1000 parts of a solution of commercial aluminum 65 Example 32 ethylate in ethyl acetate (2.7 percent of aluminum) 60 In 460 parts of a solution of commercial aluminum parts of phthalimide are added, while stirring. The mix ethylate in ethyl acetate (2.2 percent of aluminum), ture is boiled for 1 hour under reflux. Ethanol is split obtained by the process described in German Patent No. off and a clear solution of the condensation product of 386,688, 62 parts of sperm oil fatty acid (acid number aluminum ethylate and phthalimide is formed. The sol 70 212, saponification number 214, iodine number 71) are vent is distilled off and a brittle resin is obtained which dissolved, while stirring. After 10 hours the reaction is soluble in anhydrous alcohol, xylene and perchlor product has deposited as an oil which is separated by ethylene. means of a separating funnel. 160 parts of a yellowish When proceeding in the same manner but using, in oil are obtained which is soluble in cold carbon tetra stead of phthalimide, 40 parts of succinimide or 100 parts 75 chloride, benzene, and benzine. 2,844,551 15 . . . . . 16. Example 33 is likewise soluble in aromatic and aliphatic hydrocar - 40 parts of aluminum ethylate" are boiled for 1 night bons and chlorinated hydrocarbons. under reflux with 240 parts of nearly anhydrous alcohol Example 36 (0.7 percent of water), as described by Bersin (Diss. To 84 parts of the solution of aluminum ethylate Konigsberg, 1928, page 22), whereby a clear solution used in the process described in Example 35-9 parts of an aluminum ethylate of the analytic composition of glacial acetic acid are added dropwise, while stir Al(OCH5)2.1 is obained. In this hot solution 56 parts ring. Sight spontaneous heating takes place, and a of commercial stearic acid (molecular weight 280, so : clear solution of the condensation product of aluminum lidification point 52° C.) are dissolved, while stirring, O ethylate and acetic acid is formed which is further stirred at 60° C., and the clear solution of the condensation for 1 hour at 50° C. The xylene and the ethanol, product of aluminum ethylate and commercial stearic which has been split off, are then removed by distillation acid is further boiled for 2 hours under reflux. The under reduced pressure, and the condensation product ethyl alcohol is distilled off first under atmospheric pres of aluminum ethylate and acetic acid is obtained as a sure, finally under reduced pressure. The condensation 15 solid white resin; it is soluble in anhydrous ethanol and product of aluminum ethylate and commercial stearic methanol. acid is obtained as a viscous oil which solidifies, on When proceeding in the same manner but using, cooling, in the form of a wax readily soluble in carbon instead of glacial acetic acid, a solution of 18 parts tetrachloride and benzene. -- a When proceeding in the same manner but using, in of benzoic acid or 25 parts of ortho-chlorobenzoic acid stead of stearic acid, a commercial sperm oil fatty acid 20 in 60 parts of alcohol, the condensation product of alu (acid number 210, saponification number 212, iodine minum ethylate and benzoic or ortho-chlorobenzoic acid number 90) or a naphthenic acid (acid number 230), is obtained in the form of a resin. the condensation product of aluminum ethylate and sperm Example 37 oil fatty acid or naphthenic acid is obtained as a viscous 25 221 parts of a di-(chloroethylate) of aluminum chlo oil readily soluble in carbon tetrachloride and benzene. ride of the formula AlCl(OCHC), obtained by re Example 34 action of 1 mol of aluminum chloride in diethyl ether with 2 mols of ethyleneoxide are dissolved in 200 parts 400 parts of a solution of readily soluble aluminum of benzene, and 140 parts of stearic acid (molecular butylate of the analytic composition Al(CHgO)2.6, ob weight 280, solidification point 54 C.) are then added, tained by reaction of 20 parts of aluminum powder with while stirring. While heating to 80 C., gaseous hydro 133 parts of n-butanol (content of water=2 percent) in chloric acid is separated, and a clear solution of the 260 parts of boiling xylene are reacted with 95 parts of condensation product of aluminum chloroethylate and benzenesulfinic acid, while stirring, at 50 C. A clear stearic acid is formed. The xylene is distilled off and solution of the condensation product of aluminum butyl 35 the condensation product is obtained as a viscous oil ate and benzenesulfinic acid is obtained. After heating which, on cooling, solidifies slowly to yield a tough wax for 1 hour at 80° C., the xylene and the eliminated soluble in aliphatic and aromatic hydrocarbons and halo butanol are distilled off under reduced pressure. The genated hydrocarbons. condensation product of aluminum butylate and benzene When proceeding in the same manner but using 240 sulfinic acid is obtained as a soft resin which is soluble parts of stearic acid or 150 parts of lauric acid, the in aromatic hydrocarbons, aliphatic esters and aliphatic 40 condensation product of aluminum chloroethylate and chlorinated hydrocarbons. a 8 When proceeding in the same manner but using, in stearic or lauric acid is obtained in the form of a wax stead of benzenesulfinic acid, 94 parts of cyclohexane like substance having a better solubility. sulfinic acid or 78 parts of para-toluenesulfinic acid or 45 Example 38 200 parts of alkylsulfinic acid of an average molecular 180 parts of di-isopropylate of aluminum chloride, weight of 280 (obtained in known manner from Fischer obtained by reaction of 1 mol of acetyl chloride with Tropsch hydrocarbons (distilling at a temperature be aluminum isopropylate, are dissolved, while stirring, at tween 230° C. and 320° C., and having an average about 50° C. in 720 parts of xylene, and 140 parts of molecular weight of about 220, and an average chain 50 stearic acid (molecular weight 280, solidification point length of about Cis), by semisulfochlorination, reaction 53 C.) or oleic acid are dissolved in this solution. The with sodium sulfite and separation of the unsaponifiable resultant xylene solution of the condensation product matter, the condensation product of aluminum butylate of the di-isopropylate of aluminum chloride and stearic and cyclohexane- or para-toluene- or alkyl-sulfinic acid or oleic acid is heated for 1 hour at 90° C., and the is obtained as a soft resin soluble in Xylene. 55 solvent is then distilled off under reduced pressure. A Example 35 viscous oil is obtained as residue which, on cooling, 84 parts of a solution of aluminum ethylate of the solidifies slowly in the form of a very soft wax, which analytic composition Al(OC3H5)2.3, obtained by re is soluble in aliphatic and aromatic hydrocarbons, action of 40 parts of aluminum powder with 190 parts chlorinated hydrocarbons, ethyl acetate and alcohol. of ethanol of 95 percent strength in 500 parts of boil 60 When proceeding in the same manner but using 252 ing xylene, are stirred, at room temperature, with 35 parts of stearic acid or 300 parts of montanic acid parts of palmitic acid. When the stearic acid has been (molecular weight 335), a hard wax of the same prop dissolved, the clear yellowish solution of the condensa erties of solubility is obtained. tion product of aluminum ethylate and palmitic acid Example 39 is heated at 70° C. for 1 hour. The Xylene and the 65 eliminated ethanol are then distilled off, first at room 270 parts of a xylene solution of aluminum ethylate temperature, finally under reduced pressure, and the con (5 percent of aluminum), obtained from 160 parts of densation product is obtained in the form of a viscous aluminum powder and 640 parts of ethanol of 95 per oil, which solidifies, on cooling, in the form of a soft cent strength in 1860 parts of boiling xylene, are mixed wax which is readily soluble in aromatic and aliphatic 70 with 200 parts of anhydrous alcohol, and 70 parts of hydrocarbons and chlorinated hydrocarbons. commercial stearic acid (molecular weight 270, solidifi When proceeding in the same manner but using, in cation point 52 C.) are dissolved therein, while stir stead of palmitic acid, 40 parts of commercial stearic ring, at about 30° C. Into this clear solution of the acid (molecular weight 275, solidification point 53 C.) condensation product of aluminum ethylate and com or colophony, a brittle, elastic wax is obtained which 75 mercial stearic acid there is poured, while stirring, a 2,844,551 7 8 solution of 60 parts of alkylsulfonic acid in 200 parts In the same manner a stabilized solution of the con of absolute alcohol. This acid of the molecular weight densation product of aluminum isopropylate and oleic of about 300 was obtained by subjecting a mixture of acid can be obtained. Fischer-Tropsch hydrocarbons-distilling at a temper ature between about 230 C. and about 320 C. and 5 Example 44 having an average molecular weight of about 200-to semisulfochlorination, hydrolysis and separation of the 110 parts of a solution of commercial aluminum ethyl unsaponifiable matter. While stirring for 1 hour at 75 ate in ethyl acetate (2.2 percent of aluminum), obtained C., a clear solution of the condensation product of by the process described in German Patent No. 386,688, stearic aluminum ethylate and alkylsulfonic acid is ob are reacted at about 50° C. with 11 parts of stearic acid tained. The solvent is distilled off under reduced pres and, the reaction terminated, about half of the ethylace sure, and the condensation product is obtained in the tate is distilled off at about 50 C. under reduced pres form of a brittle resin which is soluble in aliphatic and sure. 4 parts of acetoacetic ester are then added to the aromatic hydrocarbons and halogenated hydrocarbons. solution, while stirring, and the ethyl acetate still present When proceeding in the same manner but using, in is distilled off, at 70° C. and under a pressure of about stead of 60 parts of alkylsulfonic acid, 30 parts of para 100 millimeters of mercury. . . toluenesulfonic acid, a resin of similar properties is ob By this method the condensation product of the alumi tained. num ethylate and stearic acid is obtained in the form Example 40 of a viscous oil which slowly solidifies, in the cold, to yield a softwax. First, a xylene solution of acetic aluminum ethylate is 20. The compound obtained is soluble in aliphatic and aro prepared as described in Example 36. 6 parts of Stearic matic hydrocarbons, chlorinated hydrocarbons and ethyl acid are then added, while stirring, at 50° C., and the acetate and is stable against moisture. solution is heated for 1 hour at 70° C. The solvent is When proceeding in the same manner but using, in then distilled off under reduced pressure, and the con 25 stead of stearic acid, the corresponding amount of com densation product of acetic aluminum ethylate and mercial sperm oil fatty acid (acid number 212, saponifica stearic acid is obtained in the form of a tough wax which tion number 214, iodine number 71), the stabilized con is soluble in aliphatic and aromatic hydrocarbons and densation product of aluminum ethylate and sperm oil chlorinated hydrocarbons. fatty acid is obtained as a viscous oil which is soluble When proceeding in the same manner but using, in 30 in carbon tetrachloride and xylene. stead of acetic acid the corresponding amount of chloro acetic acid, formic acid or propionic acid, a wax-like resin Example 45 soluble in xylene is likewise obtained. To 540 parts of a solution of commercial aluminum Example 41 ethylate (2.5 percent of aluminum) in ethyl acetate, ob 400 parts of the xylene solution of aluminum-n-butylate, 35 tained by the process described in German Patent No. as described in Example 34, are mixed, while stirring, 386,688, 12 parts of glacial acetic acid are added drop with 400 parts of n-butanol; 100 parts of phthalic an wise, while stirring, at about 20° C., 54 parts of stearic hydride are added, and the mixture is heated to 70° C. acid (molecular weight 270, solidification point 53 C.) A clear solution of the condensation product is obtained. are then added and the whole is stirred at 60° C. for 1 After heating for 1 hour at 90° C., the solvent is distilled O hour. From the clear solution of the condensation prod off under reduced pressure, and a sticky resin is obtained uct of acetic aluminum ethylate and stearic acid obtained which is soluble in xylene and perchloroethylene. the solvent is removed by distillation, and a soft resin is When proceeding in the same manner but using, instead obtained as residue. In order to stabilize this resin against of phthalic anhydride, 125 parts of 4-chlorophthalic an moisture, it is dissolved in 10 times its weight of methyl hydride, a resin is obtained which is likewise soluble in ene chloride, 22 parts of acetoacetic ester are added, and Xylene and perchloroethylene. the solution is heated to 40° C. for 15 minutes. The methylene chloride is distilled off and the stabilized con Example 42 densation product, free from solvent, is obtained in the 10 parts of acetylacetone are added to a solution of 50 form of a soft wax which is soluble in benzene, carbon 100 parts of the condensation product of aluminum ethyl tetrachloride and test benzine, and is stable against mois ate and stearic acid in 2000 parts of carbon tetrachloride. ture. The condensation product has been obtained by reacting When instead of acetoacetic ester, the corresponding 0.9 mol of stearic acid with 1 mol of aluminum ethylate. amount of acetylacetone, acetonitrile or nitromethane is The stabilizing effect is seen from the behavior of the 55 used for the stabilizing process, stabilized condensation solution on addition of aqueous alcohol. Whereas a non products of acetic aluminum ethylate and stearic acid stabilized solution remains clear after addition of absolute of analogous properties are obtained. alcohol, basic aluminum stearate is separated when al cohol of 96 percent strength or more hydrous alcohol Example 46 is added. Under the same conditions, however, no basic 60 In 160 parts of aluminum ethylate, dissolved in 1000 aluminum stearate is separated from the stabilized solu parts of xylene, 100 parts of benzoic acid are dissolved, tion. while stirring, at about 50 C. To the clear solution of When using, instead of acetylacetone, 25 parts of the condensation product of aluminum ethylate and acetoacetic ester, the same effect is obtained. benzoic acid obtained 65 parts of acetoacetic ester are Example 43 added and stirring is continued for 15 minutes at about A xylene solution of 1 mol of aluminum isopropylate 60° C. By this operation a solution of the condensation. is reacted at about 50 C. with 0.65 mol of stearic acid product of aluminum ethylate and benzoic acid is obtained and the whole is heated to 90° C. To the resultant solu which is stable against moisture. The solvent is distilled tion of the condensation product of aluminum isopro 70 off under reduced pressure and the condensation product pylate and stearic acid 0.3 mol of acetoacetic ester or is obtained in the form of a soft resin which is free acetylacetone is subsequently added, and the solution from solvent and soluble in carbon tetrachloride and , is heated for 4 hour at 60° C. The solution of the con benzene. densation product of aluminum isopropylate and stearic Example 47 acid so obtained is stable against atmospheric moisture. 75 20 parts of aluminum isopropylate are dissolved in 100 2,844,551 9 2) parts of benzene, and the compound is stabilized against about 40 C. to 140° C. an: aluminum alcoholate con moisture by addition of 2.5 parts of acetylacetone while taining up to four carbon atoms in the alcohol radicals heating to 50° C. for a short time. The stabilization with less than the equimolar amount of a monobasic is demonstrated by the fact that from a test portion to organic acid capable of forming salts with aluminum, which isopropanol of 95. percent strength has been added ) whereby a primary-monosalt of the aluminum alcoholate aluminum hydroxide is no longer precipitated. In the soluble in said inert organic solvent is first formed stabilized benzene solution so obtained 14 parts of stearic and the monosalt reacts further with the excess alcoholate acid (molecular weight 270, solidification point 52° C.) to form acid aluminum alcoholates also soluble in said are dissolved, while stirring, at about 50° C., and the inert organic solvent. clear solution is heated to 80° C. for 4 hour. The O 4. The process for preparing high molecular acid solvent is distilled off under reduced pressure, and the aluminunn alcoholates containing less than one acid stabilized condensation product of aluminum isopropylate radical per aluminum atom which comprises reacting at and stearic acid is - obtained in the form of a soft wax a temperature ranging from about 40 C. to 140 C. which is a soluble in... xylene, carbon tetrachloride and an aluminum alcoholate containing up to four carbon test-benzine. atoms in the alcohol radicals with less than the equimolar Example 48 amount of a monobasic organic acid capable of forming salts with aluminum, whereby a primary monosalt of the To 100 parts of a solution of commercial aluminum aluminum alcoholate is first formed and the monosalt ethylate in ethyl acetate (2.7 percent of aluminum), reacts further with the excess alcoholate. obtained according to the process described in German 5. The process defined in claim 4, wherein the alumi Patent No. 386,688, 6 parts of acetoacetic ester are num alcoholate on the average contains less than 1 added dropwise and the product is stabilized against organic radical bound to the aluminum atom through moisture by heating for /2 hour to about 40° C. The an oxygen atom. stabilization is demonstrated by the fact that, from a 6. The process defined in claim 4, wherein the reaction test portion to which alcohol - of 96 percent strength is effected in the presence of an aliphatic volatile complex has been added aluminum hydroxide is no longer precip forming organic compound selected from the group itated. ... 10 parts of benzoic acid are then added, while consisting of lower alkyl esters of aliphatic hydroxy stirring. The clear, mixture is boiled for 2 hour under carboxylic acids, oximes of carbonyl-substituted alkanes, reflux, and the solvent is distilled off under reduced compounds containing a group capable of desmotropic pressure. The condensation product, of stabilized alu 30 rearrangement to the aci-form, compounds containing minum ethylate and benzoic acid is obtained as a residue a reactive methylene group, hydroxy-oxo-compounds, in the form of a resin which is soluble in alcohol. and aliphatic nitriles, whereby the acid aluminum alco When proceeding in the same manner but using, holates are stabilized against moisture. instead of benzoic acid, 18 parts of lauric acid, the 7. The process defined in claim 4, including the further stabilized condensation product of aluminum ethylate 35 step of adding an aliphatic volatile complex forming and lauric acid is obtained as a soft wax which is soluble organic compound selected from the -group consisting of in carbon tetrachloride, test benzine and benzene. lower alkyl esters of aliphatic hydroxycarboxylic acids, oximes of carbonyl-substituted -alkanes, compounds con Example 49. taining a group capable of desmotropic rearrangement To 510 parts of the stabilized solution of aluminum 40 to the aci-form, compounds containing a reactive ethylate, described in Example 48, 12 parts of glacial methylene group, hydroxy-oxo-compounds, and aliphatic acetic acid are added dropwise, while stirring, at about nitriles, whereby the acid aluminum alcoholates are 20° C., and 60 parts of stearic acid are dissolved therein, stabilized against: moisture. while stirring, at about 50° C. The solvent is distilled 8. The process defined in claim 4, wherein the mono off, finally under reduced pressure, from the clear solu 45 basic organic acid is a monocarboxylic acid. tion of the stabilized condensation product of acetic 9. The process defined in claim 4, wherein the mono aluminum ethylate and stearic acid, and a soft resin is basic organic acid is an aliphatic monocarboxylic acid. obtained which is soluble in carbon tetrachloride and 10. The process defined in claim 4, wherein the mono xylene. basic organic acid is a higher aliphatic monocarboxylic When proceeding in the same manner but using, instead 50 acid. of glacial acetic acid, the corresponding amount of formic 11. The process defined in claim 4, wherein a part of acid or, instead of stearic acid, the corresponding amount the monobasic. organic acid is added at a low temperature of sperm oil fatty acid, the same results are obtained. to a solvent containing the aluminum alcoholate, and We claim: then the balance of the acid is added while the tempera 1. The process for preparing stable high molecular 5 5 ture is raised between 0° C. to 40°C. above said low acid aluminum alcoholates containing less than one acid temperature. radical per aluminum atom which comprises reacting 12. The condensation product produced in accordance 1 mol of an aluminum alcoholate with less than one with the process of claim 4. mol of a monobasic organic acid capable of forming 13. The process for preparing high molecular acid salts with aluminum at a temperature ranging from 60 aluminum alcoholates containing less than one acid radical about 40°C. to 140° C. and in the presence of a lower per aluminum atom which comprises reacting in the alkyl ester of an aliphatic hydroxycarboxylic acid as a absence of a solvent at a temperature ranging from about volatile complex forming organic compound. 40° C. to 140 C. a molten aluminum alcoholate con 2. The process for preparing stable high molecular taining up to four carbon atoms in the alcohol radicals acid aluminum alcoholates containing less than one acid with less than the equimolar amount of a monobasic radical per aluminum atom which comprises reacting organic acid capable of forming salts with aluminum, mol of an aluminum alcoholate with less than one mol whereby a primary monoSalt of the aluminum alcoholate of a monobasic organic acid capable of forming salts is first formed and the monosalt reacts further with the with aluminum at a temperature ranging from about 40 excess alcoholiate. C. to 140 C. and in the presence of an oxime of a 14. The process defined in claim 4 wherein the entire carbonyl-substituted alkane. amount of monobasic organic acid is added at a tempera 3. The process for preparing high molecular acid ture below 40° C. to a solvent containing the aluminum aluminum alcoholates containing less than one acid radical per aluminum atom which, comprises contacting in an alcoholate, and the reaction mixture is thereafter heated. inert, organic solvent at a temperature ranging from 75 (References -on following page) 2,844,551 21 22 References Cited in the file of this patent OTHER REFERENCES UNITED STATES PATENTS Eigenberger: "Fette und Seifen.” Heft 7, July (1942), 2,582,833 Hunn ------a" ', 19 pp.gray 505-508. is Physical and Coloid Chem, vol. 53 (1949), pp. 23-38. FOREIGN PATENTS Parry et al.: “Trans. Faraday Soc.” 46 (1950), pp. 503,437 Belgium ------June 15, 1951 305-10.